JPH02310555A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain high-contrast photographic characteristics by incorporating at least one kind of specified compd. and at least one kind of other specified compd. into an emulsion layer or a layer adjacent to the emulsion layer. CONSTITUTION:At least one kind of compd. selected among compds. represented by formulae 1-3 and at least one kind of compd. represented by formula 4 are incorporated into an emulsion layer or a layer adjacent to the emulsion layer. In the formula 1, each of R1 and R2 is aryl group or a heterocyclic group and R is an org. bonding group. In the formula 2, R21 is an aliphat., arom. or heterocyclic group, R22 is H, etc., and each of P1 and P2 is H, acyl group or sulfinic acid group. In the formula 3, Ar is a diffusion resistant group, etc., and R31 is substd. alkyl group. In the formula 4, each of R41-R46 is H, halogen, 1-23C alkyl group, nitrile group, etc. A high-contrast silver halide photographic sensitive material having superior dot quality, hardly causing fogging and also having high sensitivity is obtd.

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a silver halide photographic material that can be used to form ultra-high contrast photographic images. More specifically, the present invention relates to a silver halide photographic light-sensitive material that is highly useful in the field of photolithography and is capable of forming halftone images with high contrast using a developer with relatively good stability. [Background of the Invention] The photoengraving process includes the step of converting a continuous tone original into a halftone image, that is, the step of converting a continuous tone density change into a set of halftone dots having an area proportional to the density. include. This process uses photographic technology that can reproduce ultra-high contrast images, and involves photographing the original through an intersection screen or contact screen and forming a halftone image through contagious development. Ta. Lith-type silver halide photographic light-sensitive materials used for contagious development do not have sufficient high contrast unless they are processed with contagious developer (Lith-type developer). For example, when processed with MQ developer or PQ developer, The gamma is at most 5 or 6, and there are many 7-rings that must be avoided in terms of halftone dot formation.
It is said that it is essential to use it in combination with an infectious developer that has poor stability. Therefore, a technology was developed that uses a developing solution with a high sulfite ion concentration, good stability, and rapid processing to form ultra-high contrast images comparable to infectious development. The technique disclosed in No. 1062-44 and the like is known. In this technology, a specific compound called a high contrast agent is present in the silver halide photographic light-sensitive material, and specific silver halide grains and other photographic additives are added in order to fully exhibit the high contrast characteristics of the compound. There is a combination of C. This silver halide photographic light-sensitive material can be processed with a developer that has good preservability and can be processed quickly to obtain ultra-high contrast photographic images. During the formation of halftone dots, sandy bottle-like fog (so-called black spots) occurs, impairing the halftone image quality.To solve this problem, various stabilizers and inhibitors containing petro atoms are added. Attempts have been made to solve this problem, but it cannot be said that it has been fully resolved. [Object of the Invention] The object of the present invention is to obtain high-contrast photographic characteristics without impairing sensitivity, and to control black bins that occur in halftone images to obtain high-contrast photographic characteristics. An object of the present invention is to provide a silver photographic material. [Structure of the Invention] The above object of the present invention is to provide a silver halide photographic material having at least one silver halide emulsion layer on a support, in which the emulsion layer or an adjacent layer contains the following general formula [11,
[2],

It has been found that this can be achieved by a silver halide photographic material containing at least one compound represented by [31] and at least one compound represented by the following general formula [4]. General formula [11 (wherein, R1 and R2 represent an aryl group or a heterocyclic group, R represents an organic bonding group, n represents O to 6, m represents 0 or l, and when n is 2 or more is the general formula [21 (wherein, R2□ is an aliphatic group, aromatic group, or heterocyclic group, R12 is a hydrogen atom, WL NPI and P2 represent a hydrogen atom, an acyl group, or a sulfinic acid group.) General formula [3] % Formula % (In the formula, Ar represents an aryl group containing at least one diffusion-resistant group or silver halide adsorption promoting group, and R31 represents a substituted alkyl group.) General formula [4] R4゜ [In the formula, R, , R,2, R41, R44% R46%
R4m is a hydrogen atom, a halogen atom, and has 1 to 23 carbon atoms.
represents an alkyl group having 1 to 23 carbon atoms, an alkoxy group having 1 to 23 carbon atoms, a carboxyl group, a carboxylalkyl ester group, a hydroxyalkyl group, a hydroxyalkoxyalkyl group, a sulfo group, an amidoalkyl group, an amidophenyl group, an imidoalkyl group, and a nitrile group. ] Below, the general formula [11, [
2], [3], [4)'. This will be explained in detail. General formula [11 In the formula, R8 and R1 represent an aryl group or a heterocyclic group, R represents a divalent organic group, n is θ~6, m is O
or represents l. Here, examples of the aryl group represented by R1 and R1 include a phenyl group and a naphthyl group, and examples of the heterocyclic group include a pyridyl group, a benzothiazolyl group, a quinolyl group, and a chenyl group. Preferred is an aryl group. Various substituents can be introduced into the aryl group or heterocyclic group represented by R and R1. Examples of substituents include halogen atoms (e.g., chlorine, fluorine, etc.), alkyl groups (e.g., methyl, ethyl, dodecyl, etc.), alkoxy groups (e.g., methoxy, ethoxy, impropoxy, butoxy, octyloxy, dodecyloxy, etc.), and annulamino groups. (e.g. acetylamino, pivalylamine, benzoylamino, tetradecanoylamino, σ-(2,
4-D-L-amylphenoxy)butyrylamino, etc.]
, sulfonylamino groups (e.g., methanesulfonylamino, butanesulfonylamino, dodecanesulfonylamino, benzenesulfonylamino, etc.), urea groups (e.g., phenylurea, ethylurea, etc.), thiourea groups (e.g., phenylthiourea, ethylthiourea, etc.), hydroxy The divalent organic group represented by Examples of the group include alkylene groups (e.g., methylene, ethylene, tolyltylene, tetramethylene, etc.), arylene groups (e.g., phenylene, naphthylene, etc.), aralkylene groups, etc. Aralkylene groups include oxy groups, thio groups during bonding, etc. , a seleno group, a carboxyl group, an -N- group (Rs represents a hydrogen atom, an alkyl group, or an aryl group), a sulfonyl group, etc.
Various substituents can be introduced into the group represented by. Examples of the substituent include -C0NHNHR4 (R4 has the same meaning as R and R1 described above), an alkyl group, an alkoxy group, a halogen atom, a hydroxy group, a carboxy group, an acyl group, an aryl group, and the like. R is preferably an alkylene group. Among the compounds represented by general formula (1), preferably R1
and R7 is a substituted or unsubstituted phenyl group, and n=
A compound in which m=1 and R represents an alkylene group. , Representative compound represented by the above general formula C1) Specific compound -it tC@H+ r l -34 tC6H+ + tc6H+ + l -50 Next, to explain general formula [2], the aliphatic group represented by R21 is , preferably carbon number 6
Among the above, it is particularly a straight chain, branched or cyclic alkyl group having 8 to 50 carbon atoms. The branched alkyl group herein may be cyclized to form a saturated heterocycle containing one or more helaro atoms therein. Further, this alkyl group may have a substituent such as an aryl group, an alkoxy group, or a sulfoxy group. The aromatic group represented by R11 is a monocyclic or bicyclic aryl group or an unsaturated heterocyclic group. Here, the unsaturated heterocyclic group may be condensed with a monocyclic or bicyclic aryl group to form a heteroaryl group. Examples include a benzene ring, a naphthalene ring, a pyridine ring, a pyrimidine ring, an imidazole ring, a virolazole ring, a quinoline ring, an isoquinoline ring, a benzimidazole ring, a thiazole ring, and a benzothiazole ring, among which those containing a benzene ring are preferred. Particularly preferred as R21 is an aryl group. The aryl group or unsaturated heterocyclic group of R11 may be substituted, and typical substituents include a linear, branched or cyclic alkyl group (preferably a monocyclic alkyl group having 1 to 20 carbon atoms). or two rings), alkoxy groups (
(preferably one having 1 to 20 carbon atoms), substituted amino group (preferably an amino group substituted with an alkyl group having 1 to 20 carbon atoms), acylamino group (preferably one having 2 to 30 carbon atoms), sulfonamide Group (preferably 1 to 1 carbon atoms)
30), a ureido group (preferably a carbon number of 1 to
30). Among the groups represented by Ro in general formula [2], the optionally substituted alkoxy group has 1 to 20 carbon atoms, and may be substituted with a halogen atom, an aryl group, or the like. Among the groups represented by R1 in general formula [2], the optionally substituted aryloxy group or heterocyclic oxy group is preferably a monocyclic group, and the substituents include a halogen atom alkyl group, an alkoxy group, Among the groups represented by R22, which include a cyano group, preferred are an optionally substituted alkoxy group or an amino group. A2 may be a cyclic structure containing an optionally substituted alkyl group, alkoxy group, or 10-1-S-1-N- group bond. However, R22 is never a hydrazino group. R11 or Ro in the general formula [1] may have a ballast group commonly used in immobile photographic additives such as couplers incorporated therein. The ballast group is a group having a carbon number of 8 or more and is relatively inert to photography, such as an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a fninoxy group,
It can be selected from alkylphenoxy groups, etc. R2 or R22 in the general formula [2] may have a group incorporated therein that enhances adsorption to the silver oxide grain surface. Such syringe groups include the groups described in US Pat. No. 4,355.105, such as thiourea groups, heterocyclic thioamide groups, mercapto heterocyclic groups, and triazole groups. Among the compounds represented by the general formula [2], the compounds represented by the following general formula [2-al] are particularly preferred. General formula [2-al In the above general formula [2-al, R13 and R21 are hydrogen atoms, optionally substituted alkyl groups (e.g. methyl group, ethyl group, butyl group, dodecyl group, 2-hydroxypropyl group, -cyanoethyl group, 2-chloroethyl group), optionally substituted phenyl group, naphthyl group, cyclohexyl group, pyridyl group, pyrrolidyl group (e.g. phenyl group, p-methylphenyl group, naphthyl group, α-hydroxynaphthyl group, cyclohexyl group) group, p-methylcyclohexyl group, pyridyl group, 4-propyl-2-pyridyl group, pyrrolidyl group, 4-methyl-
2-pyrrolidyl group), RXm is a hydrogen atom or an optionally substituted benzyl group,
Alkoxy and alkyl groups (e.g. benzyl, p-
methylbenzyl group, methoxy group, ethoxy group, ethyl group, butyl group), R8 and R37 represent a divalent aromatic group (e.g. phenylene group or styrene group),
Y represents an atom or an oxygen atom, and L represents a divalent bonding group (e.g. -SO, ClICH2N1(-3o, NHl
-OCR, So, NH, -0-1-CH=N-), R1, represents -R/R// or -0R8, R/,
R1/ and Rzs are hydrogen atoms, optionally substituted alkyl groups (e.g. methyl group, ethyl group, dodecyl group), phenyl groups (e.g. phenyl group, p-methylphenyl group, p
-methoxyphenyl group), naphthyl group (e.g. gunaphthyl group, β-naphthyl group) or heterocyclic group (e.g. unsaturated heterocyclic group such as pyridine, thiophene, furan, or saturated heterocyclic group such as tetrahydrofuran, sulfolane). Represents a cyclic group, and R' and R//R may form a ring (for example, piperidine, piperazine, morpholine, etc.) together with a nitrogen atom. m and n represent 0 or 1. When R2mOR2m is represented, Y is It is preferable to represent a sulfur atom. Representative compounds represented by the above general formulas [2] and (2-a) are shown below. , -f General formula [2]
Specific example CF. rH. ■ *-NHNIICCOCH. CH, SoICH. C)1
,OH Sakae-st+rntcCu+. ;h=shih=sshit
t=ch=υ■L;1 H, Tori n ShiH3 η * -N) INHCCNHC+zHzs Comb 113 Next, among the above specific compounds, compound 2-45°2-4
7 will be used as an example to show its synthesis method. Synthesis of compound 2-45 Synthesis scheme (A) (B) (E) Compound 4-nitrophenylhydrazine 153g and 500g
Mix ts (l of diethyl oxalate and reflux for 1 hour. Ethanol is removed as the reaction progresses, and finally cooled to precipitate crystals. Filter, wash several times with petroleum ether, and recrystallize. Next, 50 g of the obtained crystal (A) was dissolved by heating in 1000 mff of methanol, and p
Reduction is performed under a d/C (palladium on carbon) catalyst in a H2 atmosphere pressurized at 50 Psi to obtain compound CB). 22 g of this compound (B) was added to 200 m (200 m) of acetonitrile.
and pyridine 169 at room temperature.
A solution of No. 49 in acetonitrile was added dropwise. After filtering off insoluble materials, the filtrate was concentrated and purified by recrystallization to obtain 31 g of Compound (D). Compound (D) 309 was hydrogenated in the same manner as above to obtain 20 g of compound (E). Compound (E) 109 was dissolved in 100 mQ of acetonitrile, 3.0 g of ethyl isothiocyanate was added, and the mixture was refluxed for 1 hour. After distilling off the solvent, the crystals were purified to obtain compound (F) 7.
, Oy was obtained. Compound (F) 5.0g was mixed with 5.0g of methanol.
0m12i::Dissolve methylamine (40% aqueous solution 3
m12) was added and stirred. After slightly concentrating methanol, the precipitated solid was taken out, recrystallized and purified to obtain Compound 2-45. Synthesis of Compound 2-47 Synthesis Scheme (B) (C) (D) (E) Compound 2-47 Compound (B) 229 was dissolved in 200 mff1 of pyridine, and 22 g of p-nitrobenzenesulfonyl chloride was added into a stirring vessel. . The reaction mixture was poured with water, and the precipitated solid was taken out to obtain compound (C). This compound (C) was subjected to the same reaction as compound 2-45 according to the synthesis scheme to obtain compound 2-47. Next, general formula [3] will be explained. General formula [3]. Ar NHNH-CRs+ In the general formula [3], Ar represents an aryl group containing at least one diffusion-resistant group or silver halide adsorption promoting group,
The diffusion-resistant group is preferably a ballast group commonly used in immobile photographic additives such as couplers. The ballast group is a group having 8 or more carbon atoms and is relatively inert to photography, and may be selected from, for example, an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group, an alkylphenoxy group, etc. I can do it. Examples of the silver halide adsorption promoting group include groups described in US Pat. No. 4,385,108, such as a thiourea group, a thiourethane group, a heterocyclic thioamide group, a mercapto heterocyclic group, and a triazole group. Rll represents a substituted alkyl group, and the alkyl group represents a linear, branched, or cyclic alkyl group, such as methyl, ethyl, propyl, butyl, isopropyl, pentyl, cyclohexyl, and the like. Substituents introduced into these alkyl groups include alkoxy (for example, methoxy, ethoxy, etc.), aryloxy (for example, phenoxy, p-chlorophenoxy, etc.), peterocyclic oxy (for example, pyridyloxy, etc.), mercapto, alkylthio (methylthio, ethylthio, etc.), arylthio (e.g., phenylthio, p-chlorophenylthio, etc.), heterocyclic thio (e.g., pyridylthio, pyrimidylthio, thiadiazolylthio, etc.), alkylsulfonyl (e.g., methanesulfonyl, butanesulfonyl, etc.), arylsulfonyl (e.g. benzenesulfonyl, etc.), heterocyclic sulfonyl (e.g., pyridylsulfonyl, morpholinosulfonyl, etc.), acyl (e.g., acetyl, benzoyl, etc.), cyano, chloro, bromine, alkoxycarbonyl (e.g., ethoxycarbonyl, methoxycarbonyl, etc.), aryloxycarbonyl (e.g., phenoxycarbonyl, etc.), carboxy, carbamoyl N-methylcarbamoylcarbamoyl, etc.), amino, alkylamino (e.g., methylamino, N,N-dimethylamino, etc.), arylamino (e.g., phenylamino, naphthylamino, etc.), acylamino (e.g., phenylamino, naphthylamino, etc.), For example, acetylamino, benzoylamino, etc.), alkoxycarbonylamino (for example,
ethoxycarbonylamino, etc.), aryloxycarbonylamino (e.g., phenoxycarbonylamino, etc.)
, acyloxy (e.g., acetyloxy, benzoyloxy, etc.), alkylaminocarbonyloxy (e.g., methylaminocarbonyloxy, etc.), arylaminocarbonyloxy (e.g., phenylaminocarbonyloxy, etc.), sulfo, sulfamoyl, alkylsulfamoyl (e.g. , methylsulfamoyl, etc.), arylsulfamoyl (e.g., phenylsulfamoyl, etc.)
The following groups are mentioned. The hydrogen atom of hydrazine may be substituted with a substituent such as a sulfonyl group (eg, methanesulfonyl, toluenesulfonyl group (eg, acetyl, trifluoroacetyl, etc.), oxalyl group (eg, ethoxalyl, etc.)). Representative compounds represented by the above general formula [3] include:
There are the following. Subekure*-NHNHCC1 (20C82C) I! OCR, C)
1. OHNext, a synthesis example of compound 3-5 will be described. Synthesis of Compound 3-5 Synthesis scheme Compound 3-5 was obtained according to the synthesis method of Compound 2-45.
child . General formula [
The amount of the compounds 1], [2], and [3] is 5 X 10-' to 5 X 10-' per mole of silver halide contained in the silver halide photographic material of the present invention. Preferably up to mol, more preferably 5 x 10-'l
r% L general formula [4] In the formula, R41, R4! , R43, R4, R46, Ro are a hydrogen atom, a halogen atom, an alkyl group having 1 to 23 carbon atoms, an alkoxy group having 1 to 23 carbon atoms, a carboxyl group,
It represents a carboxyalkyl ester group, hydroxyalkyl group, hydroxyalkoxyalkyl group, sulfo group, amidoalkyl group, amidophenyl group, imidoalkyl group, and nitrile group. Each of the above groups includes those having a substituent. For example, fluorinated alkyl groups, alkali metal-substituted sulfo groups,
etc. can be used. Next, [exemplary compound] COOC,H, (n) C00C4H, (t
ri) COOC+oHz+(n) G
ODC, H2a(n)0CH,0C4Hs(n) CONllC+ *Hs 3(n) C0
NI'1CaH+ y(II)COOCaH+ is represented by the general formula [
The amount of compound 4] is 5XlO-' per mole of silver halide contained in the silver halide photographic material of the invention.
~, up to 5 X 10-' mol, particularly preferably 5 X
The range is preferably from 10-' to 10-2 mol. The addition time may be during the emulsion manufacturing process, but it is particularly preferable to add it during or after chemical ripening. In order to incorporate the compound of the general formula [4] of the present invention into the hydrophilic colloid layer, the compound of the general formula [4] is added by dissolving it in appropriate water and/or an organic solvent, or by dissolving it in an organic solvent. Examples include a method in which a solution is dispersed in a hydrophilic colloid matrix of gelatin or a gelatin derivative and then added, or a method in which the solution is added after being dispersed in latex. The silver halide used in the silver halide photographic material of the present invention is preferably silver chlorobromide having an AgCQ/AgBr ratio of 100/0 to 2/98;
It is preferable that the composition has a Br ratio of 90/1O to 50/50. Further, the average grain size of the silver halide grains is 0.10 μm to 0.
．． 40 μm and a monodisperse type having a variation coefficient of particle size distribution expressed by (standard deviation of particle size distribution)/(average particle size) x 100 of 15% or less is preferable. The silver halide photographic material of the present invention has at least one silver halide emulsion layer. That is, at least one silver halide emulsion layer may be provided on one side of the support, or at least one silver halide emulsion layer may be provided on both sides of the support. Then, this silver halide emulsion can be coated directly on the support, or it can be coated via another layer such as a hydrophilic colloid layer that does not contain the silver halide emulsion.
Furthermore, a hydrophilic colloid layer as a protective layer may be coated on the silver halide emulsion layer. Further, the silver halide emulsion layer may be coated separately into silver halide emulsion layers having different sensitivities, for example, high sensitivity and low sensitivity. In this case, an intermediate layer may be provided between each silver halide emulsion layer. That is, an intermediate layer made of hydrophilic colloid may be provided if necessary. Further, a non-photosensitive hydrophilic colloid layer such as an intermediate layer, a protective layer, an antihalation layer, or a backing layer may be provided between the silver halide emulsion layer and the protective layer. The compounds represented by general formulas [1], [2], [3] and general formula [4] are in the silver halide emulsion layer in the silver halide photographic light-sensitive material of the present invention or adjacent to the silver halide emulsion layer. It is included in the hydrophilic colloid layer. Next, the silver halide used in the silver halide photographic material of the present invention will be explained. Silver halide of any composition can be used. For example, silver chloride, silver chlorobromide,
There are silver chloroiodobromide, pure silver bromide, and silver iodobromide. The average diameter of the silver halide grains is preferably in the range of 0.05 to 0.5μ, and in particular, 0.
A volume of 0.40 μl is preferred. Although the particle size distribution of the silver halide grains used in the present invention is arbitrary, it is preferably adjusted so that the monodispersity value defined below is in the range of 1 to 30, more preferably in the range of 5 to 20. Here, the monodispersity is defined as the value obtained by dividing the standard deviation of particle diameter by the average particle diameter times 100. For convenience, the grain size of silver halide grains is expressed by principal in the case of cubic grains, and other grains (octahedral, tetradecahedral, etc.)
is calculated by the square root of the projected area. When carrying out the present invention, for example, silver halide grains having a multilayer structure of at least two layers can be used, for example, silver iodobromide in the core and bromide in the shell. Those consisting of silver iodobromide grains, which are silver, can be used. At this time, iodine can be contained in any layer within 5 mol%. The silver halide grains used in the silver halide emulsion of the present invention are formed by cadmium salt, zinc salt, lead salt, thallium salt, iridium salt (complex salts containing), rhodium salt, Metal ions can be added using at least one selected from salts (complex salts containing) and iron salts (complex salts containing) to contain these metal elements inside the particles and/or on the particle surfaces, and By placing the particles in a suitable reducing atmosphere, reduction sensitization can be imparted to the inside and/or the surface of the particles. Furthermore, silver halide can be sensitized by various chemical sensitizers. As the sensitizer, for example, activated gelatin, sulfur sensitizer (sodium thiosulfate, allylthiocarbamide, thiourea, allyl isothiacinate, etc.),
Selenium sensitizers (N.N-dimethylselenourea, selenourea, etc.), reduction sensitizers (triethylenetetramine, silver/tin chloride, etc.), such as potassium chlorooleite, potassium aurithiocyanate, potassium chlorooleate, 2 - Various noble metal sensitizers represented by aurosulfobenzothiazole methyl chloride, ammonium chloroparadate, potassium chlorooleate, sodium chlorovaladite, etc. can be used alone or in combination of two or more. . When using a metal sensitizer, rhodanammonium can also be used as an auxiliary agent. The silver halide grains used in the present invention can be preferably applied to grains whose surface sensitivity is higher than their internal sensitivity, so-called silver halide grains that give negative images. can be increased. Further, the silver halide emulsion used in the present invention includes mercapto compounds (1-phenyl-5-mercaptotetrazole, 2
-Mercaptobenzthiazole), benzotriazoles (5-brombenzotriazole-5-methylbenzotriazole), benzimidazoles (6-nidropenzimidazole), and the like can be used to stabilize or suppress fog. The photosensitive silver halide emulsion layer or its adjacent layer may contain research disclosure materials for the purpose of increasing sensitivity, increasing contrast, or promoting development.
Compounds described in Section XXI B-D of No. 17463 can be added. Preferably, it is a compound represented by the following general formula [5]. General formula [5] R1−〇 CH2CH, O+n H [In the formula, R1 represents a hydrogen atom or an unsubstituted or substituted aromatic ring, and n represents an integer from 1O to 200. ] Specific examples more preferable than the compound represented by the general formula [5] will be given, but the invention is not limited to these. 5-1 80(CH2Cl, 0)nHn=105
2 FIO(CHzCHzO)nHn=30
5-3 HO(CH,CB20)nl(n=5
05 4 HO(C1(2cH,0)nu
n=705 5 BP(CL(JltO)
nHn Engineering 1505 6 HO (CHzCHzO
)nHn=200 These compounds are commercially available and can be easily obtained. These compounds have a content of 0.0% per mole of silver halide. It is preferable to add 1 to 4.0 moles of O, and more preferably 0.02 to 2 moles. Further, two or more types of compounds having different values of n may be included. The silver halide emulsion used in the present invention includes a sensitizing dye,
Plasticizers, antistatic agents, surfactants, hardeners, etc. can also be added. General formulas [1], [2] according to the present invention,
When the compound [3] is added to a hydrophilic colloid layer, gelatin is suitable as the binder for the hydrophilic colloid layer, but hydrophilic colloids other than gelatin can also be used. These hydrophilic binders are preferably coated on both sides of the support at an amount of 10 g/cm2 or less, respectively. Examples of supports that can be used in carrying out the present invention include baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass plates, cellulose acetate, cellulose nitrate, and polyester films such as polyethylene terephthalate. These supports are appropriately selected depending on the intended use of the silver halide photographic material. For developing the silver halide photographic material of the present invention, the following developing agents are used, for example. Typical examples of 10- (CH= CF()n -OH type developing agents include hydroquinone, and others such as catechol and pyrogallol. Also, 80- (CH= CH)n -NH2 type developing agents Representative examples include ortho- and para-aminophenol or aminopyrazolone, including N-methyl-p-aminophenol, N-β-hydroxyethyl-p-aminophenol, p-hydroxyphenylamine acetic acid,
-Aminonaphthol etc. The hetero prototype developer includes ■-phenyl-3-pyrazolidone, l-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, l-phenyl-4 -Methyl-
3- such as 4-hydroxymethyl-3-pyrazolidone
Examples include pyrazolidones and the like. Other books include The Theory of the Photographic Process, 4th edition, by T. H. James.
ory or the Photographic P
rocess. Fourth Edition, pages 291-334 and Journal of the American Chemical Society.
rican Chemical 5ociety) Vol. 73, p. 3.100 (1951) can be effectively used in the present invention. These developers may be used alone or in combination of two or more types, but it is preferable to use two or more types in combination. I; Even if a sulfite salt such as sodium sulfite or potassium sulfite is used as a preservative in the developer used for developing the photosensitive material of the invention, the effects of the invention will not be impaired. Furthermore, hydroxylamine and hydrazide compounds may be used as preservatives. In addition, adjusting the pH with caustic alkali, alkali carbonate, or amines used in general black and white developers and providing a buffer function, and inorganic development inhibitors such as bromokali, 5-methylbenzotriazole, 5-methylbenzimidazole, 5-methylbenzotriazole, 5-methylbenzimidazole,
- organic development inhibitors such as nitroindazole, adenine, quanine, l-phenyl-5-mercaptotetrazole, metal ion scavengers such as ethylenediaminetetraacetic acid,
Development accelerators such as methanol, ethanol, benzyl alcohol, and polyalkylene oxide, surfactants such as sodium alkylarylsulfonate, natural saponins, sugars or alkyl esters of the above compounds, and hardening agents such as glutaraldehyde, pomarin, and glyoxal. agent,
It is optional to add an ionic strength adjusting agent such as sodium sulfate. The developer used in the present invention may contain alkanolamines such as jetanolamine and triethanolamine, and glycols such as diethylene glycol and triethylene glycol as organic solvents. In addition, alkylamino alcohols such as diethylamino-1,2-propanediol and butylamitubrobanol are particularly preferred [Examples] Specific examples of the present invention will be described below, but the embodiments of the present invention will be described below. Not limited. (Preparation of Silver Halide Emulsion A) A silver iodobromide emulsion (2 mol % of silver iodide per 1 mol of silver) was prepared using a simultaneous mixing method. During this mixing, Ir(Jl
, was added in an amount of 6XlO-' moles per mole of silver. The obtained emulsion was an emulsion consisting of cubic grains with an average grain size of 0.20 μm. After washing and desalting this emulsion with water in a conventional manner, the pA at 40°C was determined using an aqueous potassium iodide solution.
g was adjusted to 8.80. Further, during redispersion, a mixture of the following compounds [A], [B], and [(l) was added. [A] [B] [C] (Preparation of silver halide photographic material) Undercoat layer (JP-A-59-199
A silver halide emulsion layer having the following formulation (1) was applied on one undercoat layer of a polyethylene Tele 7 tart film having a thickness of 100 μm and coated with a gelatin amount of 2.
0g/a+", silver amount is 3.5g/+2, and then a protective layer of the following formulation (2) is coated on top of it so that the gelatin amount is 1.5g/a". , and on the other undercoat layer on the opposite side, a backing layer was applied according to the following recipe (3) so that the amount of gelatin was 2.78/fi'',
Furthermore, a protective layer of the following formulation (4) was coated on top of it so that the amount of gelatin was l, Og/+s2, and sample No.
-16 was obtained. Prescription (1) (Silver halide emulsion layer composition) Gelatin
2.0g/serve 2 Silver halide emulsion A silver amount 3.5g/a' Antifoggant=5-nitroindazole 311 stabilizer on inhibitor 4-methyl-6
-Hydroxy- 1,3,3a,7-chitrazainde 7 30+g
/a+”Surfactant: Saponin 0-1g
/m” Accelerator H(OCHxCH,), 0Hn=67.8 10
0119/II latex polymer:
0.5 g/m'' Compound according to the present invention or comparative compound Amount shown in Example 1 Sensitizing dye: Prescription (2) [Emulsion protective layer composition] Gelatin 1.5 g/m' Matting agent: Average particle size 3.0~ 5.0μm silica 0.03
g/a+” Colloidal silica 0.02g/+2
Surfactant S: C)lzcOOcHz(C2Hs)C*Hs amount C1(COOCHxCH(C*tli)Cs2-1s
O, 01g/m2 SO, Na Prescription (3) (Backing layer composition) (a) (b) (c) So, Na Gelatin 2.7g/m2 Surfactant: Saponin 0.1g/m2 Hardener: Glyoxal 0 .1g/m2 Sodium dodecylbenzenesulfonate 0.019/m" Prescription (4) [Backing protective layer composition] Gelatin Ig/+n" Matting agent: Average particle size 3. θ~5.0. um polymethyl methacrylate 0.058/ff12 Surfactant S' 0.019/In2 Hardener: Glyoxal 0.019/I11
'A halftone quality test was conducted on the obtained sample using the method described below. (Testing method for halftone dot quality) A halftone screen (150 lines/inch) with a halftone dot surface of 50% is attached to a step wedge, and the sample is placed in close contact with this screen and exposed for 5 seconds to a xenon light source. The sample was developed under the following conditions in an automatic processing machine for quick processing using the developer and fixer listed below, and the quality of the halftone dots on the sample was observed with a 100x magnifying glass.
The rank is "5", and the following are "4", "3", "2", and "1".
''. Note that the ranks rlJ and "2" are at levels that are practically unfavorable. The black pins in the halftone dots are evaluated in the same way, and the highest rank is ``5'' when there are no black pins in the halftone dots. 4",
The evaluation was performed by lowering the ranks sequentially from "3" to "2" to "l". Incidentally, in ranks "l" and "2", the black bins are also large, which is at a level that is not practical. In addition, the obtained sample was measured using a Konica digital densitometer PDP-65.
The sensitivity at 8 was measured at 10 at the concentration of sample No. 3.0.
The relative sensitivity is expressed as 0, and the gamma is expressed as the tangent between the densities 0.3 and 3.0. Developer formulation Ethylenediaminetetraacetic acid disodium salt g Sodium sulfite 609 Hydroquinone 35 g 5-Amino-I-
Pentanol 50g Potassium Bromide
2,595-Methylbenzotriazole 0.391-phenyl-3-pyrazolotone 0.29 Add water to make 1&, and adjust p)1 to 11.5 with sodium hydroxide. Fixer formulation (composition A) Ammonium thiosulfate (72.5% W/V aqueous solution) 4
0mg Sodium sulfite 17g Sodium acetate trihydrate 6.5g Boric acid
6g Sodium citrate dihydrate
2g (composition) Pure water (ion exchange water) 171112
Sulfuric acid (50% W/water solution) 4.7g
Aluminum sulfate (aqueous solution with 1103 equivalent content of 8.1% w/w)26.
When using a 5g fixer, the above compositions were dissolved in 500mR of water in the order of composition 1 and finished to 1Q before use. This fixer p
H was adjusted to 6 with acetic acid. (Development processing conditions) (Process) (Temperature) (Time) Development
40°0 15 seconds fixed
35℃ 15 Sand water washing
Dry at 30°C for 10 seconds 5
0° C. 10 seconds The following compounds (a) to (c) were used as comparative compounds added to the silver halide emulsion layer in Prescription (1) J. (a) (b) (d) The results of the above examples are shown in Table 1. As is clear from Table 1, sample No. 10 according to the present invention
-18 had high sensitivity, high contrast, and halftone dots compared to comparison Example 2 Everything was carried out in the same manner as in Example 1 except that the silver halide emulsion was changed to Emulsion B below and processing was performed with a developer having the following formulation. . The results are shown in Table 2. (Preparation of Silver Halide Emulsion B) A silver iodobromide emulsion (0.5 mol % of silver iodide per mol of silver) was prepared by a simultaneous mixing method. At the time of this mixing, 21r (
4, was added at 6X10' moles per mole of silver. The obtained emulsion was an emulsion consisting of cubic grains with an average grain size of 0.20 μm. This emulsion was washed with water and desalted according to a conventional method, and then sulfur sensitized at 62°C for 90 minutes, and the pAg at 40°C was adjusted to 7.90 with an aqueous potassium iodide solution. Developer formulation Hydroquinone 22,59 ml
0.259 Ethylenediaminetetraacetic acid 1.09 Sodium sulfite 75.0g Sodium hydroxide 7.9g Trisodium phosphate (
12 hydrate) 75, 0 g 5-methylbenzotriazole 0.25 g N% N-diethylethanolamine 12.512 Add water to make 10,
pal was adjusted to 11.6. The results of the above examples are shown in Table 2. As is clear from the results in Table 2, sample No.
As with Example 1, it can be seen that samples Nos. 28 to 36 have high sensitivity, high contrast, good halftone dot quality, and good black focus compared to Example 1. [Effects of the Invention] According to the present invention, it was possible to provide a silver halide photographic material with high contrast, excellent halftone dot quality, little capri, and high sensitivity even through rapid processing.

Claims (1)

[Scope of Claims] In a silver halide photographic material having at least one silver halide emulsion layer on a support, the emulsion layer or an adjacent layer contains the following general formulas [1], [2], [ 3] and at least one compound represented by the following general formula [4]. General formula [1] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1 and R_2 represent an aryl group or a heterocyclic group, R represents an organic bonding group, n is 0 to 6, m is 0
or 1, and when n is 2 or more, each R may be the same or different. ) General formula [2] ▲ Numerical formulas, chemical formulas, tables, etc. Represents an oxy group, an amino group, or an aryloxy group, and P_1 and P_2 represent a hydrogen atom, an acyl group, or a sulfinic acid group.) General formula [3] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, Ar represents an aryl group containing at least one diffusion-resistant group or silver halide adsorption promoting group, and R_3_1 represents a substituted alkyl group.) General formula [4] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_4_1, R_4_2, R_4_3, R_4
_4, R_4_5, R_4_6 are a hydrogen atom, a halogen atom, an alkyl group having 1 to 23 carbon atoms, an alkoxy group having 1 to 23 carbon atoms, a carboxyl group, a carboxyl alkyl ester group, a hydroxyalkyl group, a hydroxyalkoxyalkyl group, a sulfo group , represents an amidoalkyl group, an amidophenyl group, an imidoalkyl group, or a nitrile group. ]